Fiber lubricants derived from the oxyalkylation of a glycerol-1,3-dialkylether

ABSTRACT

Lubricants and processing aids for synthetic fibers, particularly polyester and nylon fibers, are disclosed comprising compounds having the structural formulas: ##STR1## in which R is an aliphatic group generally having about 3 to about 22 carbon atoms; A is a mixture of residues from ethylene oxide and at least one other lower alkylene oxide, preferably a heteric mixture of oxyethylene and oxypropylene residues in the respective ratio by weight of 20:80 to 90:10; and n has a value to produce a molecular weight of about 300 to about 3000. 
     Where liquid products are desired which contain the higher numbered carbon chain residues, low viscosity compounds can be obtained by oxyalkylating a glycerol-1,3-dialkylether with a mixture of ethylene oxide and 1,2-propylene oxide in the respective ratio as set forth above. Thus it is possible by properly balancing the carbon chain length of the R groups in the lubricant compounds of the invention with the oxyalkylene chain length to obtain products varying between water insoluble and water soluble. The oxyalkylated fiber lubricants of the invention have the properties of viscous liquids, solids or pastes at ambient temperature.

This is a division, of application Ser. No. 956,052, filed Oct. 30,1978.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the false twist processing of multi-filamentand mono-filament synthetic fibers, particularly polyester and nylonfibers with fiber processing aids applied as spin-finishes subsequent toextrusion of the fibers from the spinneret.

2. Description of the Prior Art

In the production of polyester and polyamide filament, the addition of achemical coating after extrusion from the spinneret is essential inorder to process the emerging filaments into fibers. It is known toutilize polyoxyethylene compounds as fiber lubricants as well as hetericpolyoxyalkylenes derived from the random or heteric polymerization ofethylene oxide and 1,2-propylene oxide utilizing fatty acid and fattyalcohol initiators. The fatty acid or fatty alcohol residues providelubricity and the polyoxyalkylene residues provide surface wetting andimpart water solubility to the lubricating compound.

In accordance with U.S. Pat. Nos. 2,457,139 and 2,425,755, it is knownto obtain oxyalkylated compound lubricants utilizing diols, monols, andfatty acids as polymerization initiators. Both U.S. Pat. No. 3,925,588and German Offen No. 2,516,736 disclose the heteric oxyalkylation of amixture of ethylene oxide and 1,2-propylene oxide with higher fattyacids such as stearic acid in the production of lubricants particularlyuseful in treating multi-filament polyester yarn. The hetericoxyalkylated polymer structure is known to provide liquid products atambient temperature as opposed to similar compositions obtained byoxyethylating. In U.S. Pat. No. 2,932,670 there is disclosed theethoxylation of glycerol-1,3-dialkylethers wherein the alkyl radical cancontain from 6 to 16 carbon atoms. Such compounds are disclosed as beinguseful as wetting agents and detergents. The glycerol-1,3-dialkyletherintermediates used in the preparation of the fiber lubricants of thisinvention and methods for their preparation are disclosed in KogyoKagaku Zasshi No. 64 (11), 1958-1964.

SUMMARY OF THE INVENTION

It is a primary object of this invention to provide fiber lubricatingcompounds or processing aids useful as a coating on synthetic fiberssuch as polyester or nylon fibers. The compounds have a balanced blendof lubricity in combination with the properties of water-dispersibilityor water-solubility. Said compounds can be low viscosity liquids at roomtemperature, if desired. Thus certain lubricant compounds of theinvention can be applied to the fiber, if desired, without dilution inwater since certain embodiments of the lubricants of the invention havelow viscosities at ambient temperature as compared to certain lubricantcompounds of the prior art. In addition, certain of the lubricantcompounds of the invention exhibit the characteristic of selfemulsification and others exhibit the characteristic of water solubilityat ambient temperatures thus allowing application of these lubricants totextile fibers by utilizing aqueous dispersions, emulsions or solutionsof the lubricant compounds.

These and other objects are accomplished in accordance with thisinvention by utilizing lubricant compounds derived from an intermediatecompound obtained by the reaction of an epihalohydrin, preferablyepichlorohydrin, with a fatty alcohol. Such intermediates have thestructural formula: ##STR2## wherein R is derived from the residue of astraight or branched chain aliphatic alcohol. The hydroxyl group in thecenter of the molecule is reactive in an oxyalkylation reaction. Uponoxyalkylation of this intermediate with either (1) ethylene oxide or (2)a mixture of ethylene oxide and at least one other lower alkylene oxide,preferably 1,2-propylene oxide, so as to obtain a polyoxyalkylated chaincontaining heteric or random groups of the residues thereof, thefollowing compounds are obtained: ##STR3## wherein R is a straight orbranched chain aliphatic radical generally having about 3 to about 22carbon atoms; A is preferably a mixture of oxyethylene and oxypropyleneresidues in the respective ratio by weight of 20:80 to 90:10; and n hasa value to produce a molecular weight of about 300 to about 3000.

The lubricant compositions of the invention provide an improved balanceof lubricity and wetting ability derived from the fact that thehydrophile oxyalkylene groups are attached to the center of thehydrophobic portion of the lubricant molecule.

DETAILED DESCRIPTION OF THE INVENTION AND OF THE PREFERRED EMBODIMENTS

The lubricant compounds of the invention provide a novel biodegradablefiber lubricant which overcomes certain of the difficulties generallyassociated with textile fiber lubricants. For instance, where mineraloil or a fatty acid ester such as butyl stearate is utilized incombination with other components as a fiber lubricant, suchcompositions are difficult to apply to the fiber since the compositionsrequire the use of an emulsifier such as a nonionic or anionicemulsifier and there is a tendency toward nonuniformity of theapplication of the fiber lubricant to the fiber under thesecircumstances. In addition, such compositions utilizing mineral oil orfatty acids esters are not easily biodegraded and thus represent apollution problem in the sense that an oil film or sludge is dischargedinto surrounding rivers and waterways adjacent to the textile factorywhere such lubricants are utilized.

Where the fiber lubricant contains a polyoxyalkylated fatty alcohol orfatty acid, it is possible to provide self-emulsifying or water-solublelubricating compositions so that the appearance of rivers or surroundingwaterways contaminated with such compounds is not seriously affected.Nevertheless these compounds are not readily subject to biodegradation,a general characteristic of compounds which include a polyoxyalkylenechain in the molecule.

The compounds of the invention while containing polyoxyalkylene chainsin the molecule are unique in that the polyoxyalkylene chains areattached to the hydrophobe in the center thereof providing a morereadily biodegradable fiber lubricating compound which can be attackedby bacteria on either end of the chain of the hydrophobe thus eventuallybreaking up the polymer into smaller components which can be morereadily biodegraded.

Another drawback of certain of the prior art lubricants is that it isdifficult to incorporate the higher fatty acid or alcohols in the fiberlubricant compound and yet obtain compounds having low viscosity whichwill permit ease of application to the textile fiber as well as animproved lubricating effect. The compounds of the invention overcomethis disadvantage since compounds of the invention can be oxyalkylatedwith a relatively small amount of ethylene oxide in comparison with therelatively long chains on the hydrophobe thus maintaining the viscosityof the lubricant compound either as a liquid at ambient temperature oras a paste. Alternatively, where the lubricant compound of the inventionis oxyalkylated utilizing, for instance, a mixture of ethylene oxide and1,2-propylene oxide similarly long carbon chains can be utilized as thehydrophobe together with a relatively long oxyalkylene chain. Thepreferred mixture of ethylene oxide and 1,2-propylene oxide is employedin a ratio so as to maintain a suitable balance in the compound betweenthe desired water-solubility or self-emulsification characteristics andlow viscosity at ambient temperature.

The fiber lubricants of the invention are prepared by the ethoxylationor mixed oxyalkylation of an intermediate compound which is obtained byreacting an epihalohydrin, preferably epichlorohydrin, with a straightor branched-chain fatty alcohol. Useful mixed alkylene oxides which canbe employed in the preparation of the oxyalkylene copolymer fiberlubricants of the invention are mixtures of ethylene oxide and anotherlower alkylene oxide. Generally, 1,2-propylene oxide, butylene oxide,and hexylene oxide can be employed in admixture with ethylene oxide inthe preparation of said fiber lubricants. Both block and hetericcopolymers are useful but, preferably, the fiber lubricants of theinvention are derived from the reaction of mixtures of ethylene oxideand 1,2-propylene oxide. The intermediate obtained is a diethercontaining a single hydroxyl group located in the center of themolecule. The glycerol-1,3-dialkylether intermediate can be prepared byreacting epichlorohydrin with a straight chain or branched chainaliphatic alcohol in the presence of an alkali metal, for instancesodium. Best results are obtained by the addition of the epichlorohydrindropwise to a large excess of alcohol containing a slight molar excessof alkali metal based upon the epichlorohydrin. The rate of addition issuch as to control the exotherm of the reaction at a temperature suchthat a minimal quantity of tarry products are obtained.

Alternatively, said intermediate compound can be formed by reactingepichlorohydrin with straight chain or branched alcohol catalyzed withBF₃ etherate or similar Lewis acid. Upon base treatment, the alkoxyglycidyl ether is formed which can then be added to a large excess ofalcohol catalyzed with BF₃ etherate or similar Lewis acid to obtain theproduct. By using a different alcohol in the first and third step, amixed glycerol-1,3-dialkylether intermediate can be prepared. Both ofthese preparations, base catalyzed and Lewis acid catalyzed, yield sometetraether which can be removed by distilling off theglycerol-1,3-dialkylether intermediate or can be left mixed with theintermediate for conversion to the fiber lubricants of this invention.

Representative useful straight chain or branched chain fatty alcoholsgenerally contain about 3 to about 22 carbon atoms, preferably about 10to about 22 carbon atoms, and most preferably about 12 to about 22carbon atoms in the chain and are as follows: butyl, pentyl, hexyl,heptyl alcohols, octyl alcohol, methylisobutyl carbinol, decyl alcohol,cetyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, and stearylalcohol. The fatty alcohols are available commercially as mixtures offatty alcohols such as mixtures of fatty alcohols having carbon chainlengths ranging between about 12 and about 15, as represented by thecommercially available products sold under the trademark "NEODOL 25" orthe fatty alcohol blend sold under the trademark "EPAL 12/85" which is amixture of fatty alcohols in which the fatty alcohol having a 12 carbonchain predominates to the extent of 85 percent. While epichlorohydrin isthe preferred reactant for the production of theglycerol-1,3-dialkylethers other epihalohydrins can be utilized such asthe bromo and fluoro epihalohydrins.

In general the fiber lubricants of the invention exhibit a desirablebalance of properties including biodegradability andself-emulsifiability in water together with low viscosity at ambienttemperature. The oxyalkylated fiber lubricant products of the inventionare generally fluids at ambient temperature. Because the fiberlubricants of the invention can be easily prepared so as to contain twofatty alcohol chain residues instead of one as in the prior art fiberlubricants of the invention prepared by the ethoxylation or alkoxylationof fatty alcohols or fatty acids, the fiber lubricants of the inventionexhibit excellent lubricity characteristics while at the same timeretaining the characteristics of fluidity at ambient temperature andbeing either self-emulsifiable or water-soluble.

The low viscosity of the fiber lubricants of the invention make itpossible to apply them to the fibers without dilution by passing thefibers through a trough or having the fibers make contact with a "kiss"roll rotating in a trough in which the fiber lubriants are contained.The fiber lubricants of the invention can also be similarly applied tothe fibers after dilution with water. Generally, about 0.1 percent byweight to about 1.5 percent by weight, preferably about 0.1 percent toabout 1 percent by weight, of the fiber lubricants of the invention,based upon the weight of the fibers, are applied to thermoplasticsynthetic fibers to improve the lubricity thereof.

The water-solubility or water-dispersibility of the fiber lubricants ofthe invention facilitates the subsequent scouring operation utilized toremove the lubricant subsequent to the mechanical and heat treatment ofthe yarn prior to the dyeing operation. In addition the water-solubilityor self-emulsifiability of the fiber lubricants of the invention aid indisposal of these materials by the textile mill usually preventing theaccumulation of an oil film or slick in nearby streams or ponds as wouldbe the case with a mineral oil-based fiber lubricant of the prior art.While the mineral oil type fiber lubricants would be very slowlydecomposed by bacteria subsequent to disposal, the nature of the fiberlubricants of the invention permit biodegradation to take place readily.

The fiber lubricants of the invention have excellent stability tosmoking under conditions of use at elevated temperature in themechanical and heat treatment operation subsequent to extrusion of thefiber, as compared to prior art ethoxylated and alkoxylated fatty acidsand fatty alcohols as well as mineral oils utilized in the prior art.Additional high temperature stability of the fiber lubricants can beobtained by the addition of conventional stabilizers and anti-oxidantsas is known in the art.

The following test methods were used in evaluating the suitability asfiber lubricants of the compounds of the instant invention.

The thin film smoke point of fiber lubricants of the invention wasevaluated by inserting about 0.5 gram of lubricant into a machineddepression (so as to fill the depression) on one face of a stainlesssteel cylinder measuring 1 inch by 25/8 inches in diameter. The cylinderhas a drilled opening on its side into which about one inch of the bulbend of a glass laboratory thermometer is inserted in order to determinethe temperature of the cylinder. The machined depression on one face ofthe cylinder is 1/16 inch deep and extends over the whole face of thecylinder except for a 5/16 inch lip around the perimeter of thecylinder. The assembly is heated from below with a bunsen burner at arapid rate of heating to determine the approximate, or initial, smokepoint which is the temperature at which smoke first appears when theassembly is viewed against a dark background. Thereafter, the smokepoint is redetermined using a slow rate of heating of about 5°-10° C.per minute in the vicinity of the initial smoke point.

Lubricity of polyester filament yarn having fiber lubricants of theinvention applied thereto was evaluated by applying to a scoured150-denier polyester filament producer yarn the desired percentage oflubricant. The lubricant was applied to the yarn utilizing an Atlas YarnFinish Applicator made by the Precision Machine Development Company inwhich yarn is passed at a controlled speed through a continuallyreplenished drop of finish solution of specified strength in order toachieve a uniform wetting of the yarn. The solution is metered using asyringe pump. The yarn during treatment is passed from a feeder globuleover an adjustable canter roller which functions to space the yarnfilaments for passage over a drying drum utilized in conjunction withthe application of heat in the application of the fiber lubricant to theyarn. The yarn finally is passed over a winding tube and is subsequentlyconditioned overnight under controlled conditions of temperature andhumidity (65 percent relative humidity and 70° F.) before being tested.Utilizing the fiber lubricant treated yarn, the coefficient of friction(f) was determined using a Rothschild F Meter in which the yarn ispassed over a 0.313 inch diameter satin chrome pin at a contact angle of180 degrees and at a speed of 50, 100, 150, 200, 250, and, whereverpossible, 300 meters per minute. Tensiometers on the Rothschild machinemeasure the yarn tension before and after it passes over the frictionpin so as to insure uniformity of conditions. The coefficient offriction is determined directly from the instrument chart. Forcomparison, the polyester filament yarn is measured for lubricity priorto treatment with the fiber lubricant of the invention. Test results areshown in the following Table I.

                  TABLE I                                                         ______________________________________                                        Coefficient of Friction                                                                 Coefficient of Friction (f)                                                   1% by weight lubricant on 150 denier                                          polyester yarn.                                                               Speed                                                               Lubricant   100 meters/min.                                                                             200 meters/min.                                     ______________________________________                                        Example 1   .48           .64                                                 Example 2   .37           .61                                                 Example 3   .40           .60                                                 Example 4   .40           .55                                                 No lubricant                                                                              .54           .69                                                 ______________________________________                                    

The following examples illustrate the various aspects of the inventionbut are not intended to limit it. Where not otherwise specifiedthroughout the specification and claims, temperatures are given indegrees centigrade and parts, percentages and proportions are by weight.

EXAMPLE 1

This example illustrates the preparation of a lubricant of the inventionwhich is the reaction product of 1,3-dihexoxy-2-propanol with 9 moles ofethylene oxide. The required alcohol intermediate,1,3-dihexoxy-2-propanol was prepared by the following procedure. To afive liter flask equipped with a stirring device, distillation head,condenser, temperature measuring equipment, heating mantle, andprotected with nitrogen, there was added 22.5 moles of 1-hexanol and 10grams of boron trifluoride etherate. While maintaining the temperatureat approximately 60° C., 18 moles of epichlorohydrin were slowly addedover a period of 18.5 hours. Heating was continued for an additionalfour hours to insure complete reaction and the reaction mixture wasallowed to stand for a period of 16 hours. Thereafter, 15 grams ofsodium bicarbonate were added to destroy the boron trifluoride etheratecatalyst. Thereafter, 1000 grams of the resulting crude mixture of3-chloro-1-hydroxy-2-propanol was mixed with 1000 grams of toluene and720 grams of a 40 percent aqueous solution of potassium hydroxide in afive liter flask equipped with a stirring device, temperature measuringequipment, heating mantle, and a Dean Stark trap-condenser assembly. Thereaction mixture was then heated 11.5 hours at approximately 90°-95° C.until no further water was obtained. After filtration to removepotassium chloride and distillation to remove the toluene, the crudeglycidyl ether was added over a four hour period to a round-bottom flaskcontaining 20.3 moles of hexanol and 0.22 moles of boron trifluorideetherate, said flask being maintained at approximately 60° C. andequipped with a stirring device, distillation head, condenser,temperature measuring equipment, heating mantle, and protected with anitrogen atmosphere. The temperature was then raised to 60° C. andmaintained for approximately 3.5 hours after the addition was completedto insure complete reaction. After treatment with sodium bicarbonate,filtration to remove excess hexanol, distillation and redistillation,617 grams of 1,3-dihexoxy-2-propanol was obtained in a yield of 52.2percent based upon initial epichlorohydrin utilized. The composition hada boiling point of 128° C. at 0.1 millimeters of pressure.

The fiber lubricant which is a reaction product of one mole of1,3-dihexoxy-2-propanol with 9 moles of ethylene oxide was prepared byadding 350 grams of 1,3-dihexoxy-2-propanol and 5 grams of an aqueoussolution of 45 percent potassium hydroxide to an autoclave equipped withtemperature, pressure, and vacuum controls. The autoclave was evacuatedto less than 10 millimeters of mercury while being heated to 110° C.After most of the water had been removed, the temperature was increasedto 135° C. and the autoclave was repressurized with nitrogen to 34 lbsper square inch gauge. Thereafter, 550 grams of ethylene oxide wereadded over a four hour period. The reaction mixture was then held at135° C. for an additional two hours to insure complete reaction. Theproduct was deionized to remove catalyst and the desired product wasobtained having an hydroxyl number of 87 (84 theoretical) and physicalcharacteristics as summarized in Table II and thermal characteristics assummarized in Table III.

EXAMPLE 2

This example illustrates the preparation of a lubricant of the inventionby reacting one mole of 1,3-dihexoxy-2-propanol with 8.5 moles ofethylene oxide and 1.5 moles of 1,2-propylene oxide. This lubricant wasmade utilizing substantially the same procedure as in Example 1. Thedesired product obtained after deionization had a hydroxyl number of 93(80 theoretical), physical characteristics as summarized in Table II andthermal characteristics as summarized in Table III.

EXAMPLE 3

This example illustrates the preparation of a lubricant of the inventionby the reacting of one mole of 1,3-dihexoxy-2-propanol with 12 moles ofethylene oxide and 1.5 moles of 1,2-propylene oxide. Following theprocedure of Example 1, the desired product was obtained afterdeionization with physical and thermal characteristics describedrespectively in Tables II and III.

                  TABLE II                                                        ______________________________________                                        Physical Characteristics of                                                   Fiber Lubricants of the Invention                                             Viscosity                                                                           Brookfield          Cloud Point                                                                            Surface Tension                            Ex-   at 25° C.                                                                        Saybolt   (1% wt. sol.)                                                                          (0.1% wt. sol.)                            ample (cps)     at 100° F.                                                                       (°C.)                                                                           dynes/cm                                   ______________________________________                                        1     61        151       47       26                                         2     50.5      133       23       26                                         3     81        217       54       27                                         ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Thermal Characteristics of                                                    Fiber Lubricants of the Invention                                                                 Wt. % Remaining Residue                                   Thin Film Smoke Point                                                                             at 200° C.                                         Example (°C.)    30 min.   16 hrs.                                     ______________________________________                                        1       154             14        1.7                                         2       176             1.6       0                                           3       176             1.8       0                                           4       168             65.6      19.9                                        ______________________________________                                    

EXAMPLE 4

Utilizing methods well-known to those skilled in the art, a prior artfiber lubricant was prepared, namely the laurate ester of a hetericcopolymer (30 parts by weight ethylene oxide and 70 parts by weight1,2-propylene oxide) initiated using hydroquinone of 1200 molecularweight. Thereafter, 56 parts by weight of this prior art lubricant and44 parts by weight of the heteric copolymer of Example 2 (8.5 moles ofethylene oxide and 1.5 moles of 1,2-propylene oxide) initiated with1,3-dihexoxy 2-propanol were blended. As shown in Table I, this blendhas excellent lubricity but exhibits high residue after heating (TableIII).

While this invention has been described with reference to certainspecific embodiments it will be recognized by those skilled in the artthat many variations are possible without departing from the spirit andscope of the invention and it will be understood that it is intended tocover all changes and modifications of the invention disclosed hereinfor the purposes of illustration which do not constitute departures fromthe spirit and scope of the invention.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. The process of preparinga fiber lubricating compound having the structural formula: ##STR4##wherein R is an alkyl radical having about 3 to about 22 carbon atoms; Ais a mixture of the residues of ethylene oxide and another loweralkylene oxide; n has a value to produce a molecular weight of about 300to about 3000; and said compound is the oxyalkylation product of aglycerol-1,3-dialkylether comprisinga. reacting a fatty alcohol having 3to about 22 carbon atoms with epihalohydrin catalyzed with a Lewis acidcatalyst followed by treatment with a base to form an alkoxyglycidylether, b. reacting said alkoxyglycidyl ether with an excess of a fattyalcohol having 3 to about 22 carbon atoms, wherein said alcohol can bethe same or different than said alcohol in part (a), in the presence ofa Lewis acid catalyst, c. recovering the gycerol-1,3-dialkyletherintermediate produced, and d. alkoxylating said intermediate withethylene oxide and another alkylene oxide under alkaline catalysis at atemperature of about 110° to 135° C.
 2. The process of claim 1 whereinsaid alcohol has about 10 to about 22 carbon atoms, said epihalohydrinis epichlorohydrin, and A is derived from a heteric mixture of ethyleneoxide and 1,2-propylene oxide in the respective ratio by weight of 20:80to 90:10.